TW201302879A - Thermoplastic resin composition, resin molding, and process for producing resin molding having plating layer attached thereto - Google Patents

Abstract

Provided is a thermoplastic resin molding, which has excellent bending strength, bending elastic modulus and Charpy impact strength, and on the surface of which a plating can be formed properly. A thermoplastic resin composition for laser direct structuring, which comprises 100 parts by weight of a thermoplastic resin, 10-150 parts by weight of inorganic fibers and 1-30 parts by weight of a laser direct structuring additive, wherein the laser direct structuring additive comprises at least one component selected from copper, antimony and tin and the Mohs's hardness of the laser direct structuring additive is 1.5 or more smaller than that of the inorganic fibers.

Description

Method for producing thermoplastic resin composition, resin molded article, and resin molded article with plating layer

The present invention relates to a thermoplastic resin composition for laser direct structuring (hereinafter sometimes simply referred to as "thermoplastic resin composition"). Furthermore, the present invention relates to a resin molded article obtained by molding the thermoplastic resin composition, and a method for producing a resin molded article having a plating layer on which a plating layer is formed on the surface of the resin molded article.

In recent years, with the development of mobile phones including smart phones, various studies have been conducted on methods of manufacturing antennas inside mobile phones. In particular, a method of manufacturing an antenna capable of three-dimensional design in a mobile phone is required. As one of techniques for forming such a stereoscopic antenna, laser direct structuring (hereinafter sometimes referred to as "LDS, Laser Direct Structuring") technology has attracted attention. The LDS technique is a technique in which, for example, a laser-molded article containing an LDS additive is irradiated with a laser to activate only a portion irradiated with laser light, and a metal is applied to the activated portion, thereby forming a plating layer. This technique is characterized in that a metal structure such as an antenna can be directly produced on the surface of a resin substrate without using an adhesive or the like. The LDS technology is disclosed in, for example, Japanese Patent Laid-Open Publication No. 2000-503817, Japanese Patent Laid-Open No. 2004-534408, and Japanese Patent Laid-Open No. 2004-534408.

Here, the inventors conducted research and found that, in the case of formulating an LDS additive in a thermoplastic resin formulated with inorganic fibers, although it is appropriate The plating layer is formed, but depending on the type of the LDS additive, the mechanical strength originally achieved by the inorganic fiber cannot be achieved.

The present invention has been made in an effort to solve the problems of the prior art, and an object of the invention is to provide a thermoplastic resin composition containing an inorganic fiber and an LDS additive, which can form a plating layer as appropriate and which is excellent in mechanical strength.

Based on this situation, the inventors conducted intensive studies and found that the above mechanical strength is poor because of the relationship between the inorganic fibers and the Mohs hardness of the LDS additive. The present invention has been completed based on the above findings, and specifically, the above problems are solved by the following methods.

<1> A thermoplastic resin composition for laser direct molding comprising 10 to 150 parts by weight of inorganic fibers and 1 to 30 parts by weight of a laser direct molding additive with respect to 100 parts by weight of the thermoplastic resin, and the above laser direct molding The additive contains at least one of copper, bismuth and tin and has a Mohs hardness which is 1.5 or more smaller than the Mohs hardness of the inorganic fiber.

<2> A thermoplastic resin composition for laser direct structuring according to <1>, wherein the inorganic fibers are glass fibers.

<3> A thermoplastic resin composition for laser direct structuring according to <1> or <2>, wherein the thermoplastic resin is a polyamide resin.

The thermoplastic resin composition for laser direct structuring according to any one of <1> to <3> which contains the L ^* value of 80 or more in CIELAB with respect to 100 parts by weight of the above-mentioned thermoplastic resin composition. The inorganic pigment having a hardness of 1.5 or more is 1 to 20 parts by weight smaller than the inorganic fiber.

<5> A thermoplastic resin group for laser direct structuring according to any one of <1> to <4> The compound contains 1 to 20 parts by weight of talc based on 100 parts by weight of the thermoplastic resin composition.

The thermoplastic resin composition for laser direct structuring according to any one of <1> to <4>, which contains 1 to 20 parts by weight of talc per 100 parts by weight of the thermoplastic resin composition, and the laser is directly The amount of the molding additive to be added is 1 to 15 parts by weight based on 100 parts by weight of the thermoplastic resin.

The thermoplastic resin composition for laser direct structuring according to any one of <1> to <6> wherein the inorganic fiber has a Mohs hardness of 5.5 or more, and the laser direct molding additive contains copper and Mohs hardness. It is 5.0 or less.

<8> The thermoplastic resin composition for laser direct structuring according to <7>, which further contains a base.

<9> The thermoplastic resin composition for direct laser molding of <7> or <8>, wherein the inorganic pigment has a Mohs hardness of 5.0 or less.

The thermoplastic resin composition for laser direct structuring according to any one of <7> to <9> wherein the above-mentioned laser direct structuring additive is Cu ₃ (PO ₄ ) ₂ Cu(OH) ₂ .

The thermoplastic resin composition for laser direct structuring according to any one of <1> to <6> wherein the above-mentioned laser direct structuring additive contains bismuth and tin.

<12> The thermoplastic resin composition for laser direct structuring according to <11>, wherein the above-mentioned laser direct structuring additive contains bismuth and tin, and the content of tin is more than cerium.

<13> The thermoplastic resin composition for direct laser molding of <11> or <12>, wherein the LDS additive contains an oxide containing cerium oxide and/or tin oxide.

<14> The thermoplastic resin composition for laser direct structuring according to <13>, wherein the laser direct structuring additive contains 36 to 50% by weight of (Sb/Sn)O ₂ , 35 to 53 % by weight of mica and SiO ₂ a mixture of 11 to 15% by weight of TiO ₂ .

<15> A resin molded article obtained by molding the thermoplastic resin composition for laser direct structuring according to any one of <1> to <14>.

<16> The resin molded article according to <15>, which further comprises a plating layer on the surface.

<17> A resin molded article such as <15> or <16>, which is a portable electronic machine part.

<18> A resin molded article according to <16> or <17>, wherein the plating layer has properties as an antenna.

<19> A method of producing a resin molded article with a plating layer, comprising the step of forming a resin obtained by molding a thermoplastic resin composition for direct laser molding according to any one of <1> to <14> After the surface of the molded article is irradiated with a laser, a metal is applied to form a plating layer.

<20> The method for producing a resin molded article with a plating layer according to <19>, wherein the plating layer is a copper plating layer.

<21> A method of manufacturing a portable electronic machine component having an antenna, comprising a method of producing a resin molded article having a plating layer of <19> or <20>.

According to the present invention, it is possible to provide a thermoplastic resin molded article which is excellent in bending strength, flexural modulus, and Charpy impact strength and which can form a plating layer on the surface.

Hereinafter, the contents of the present invention will be described in detail. Furthermore, in the case of this case In the above, "~" is used in the sense that the numerical values described before and after are used as the lower limit and the upper limit.

The Mohs hardness in the present invention uses a 10-stage Mohs hardness which is generally used as a hardness index of a mineral.

The thermoplastic resin composition of the present invention contains 10 to 150 parts by weight of an inorganic fiber and 1 to 30 parts by weight of an LDS additive, and the LDS additive contains at least one of copper, bismuth and tin, based on 100 parts by weight of the thermoplastic resin. And has a Mohs hardness which is 1.5 or more smaller than the Mohs hardness of the inorganic fiber.

Hereinafter, the present invention will be described in detail.

<thermoplastic resin>

The thermoplastic resin composition of the present invention contains a thermoplastic resin. The type of the thermoplastic resin is not particularly limited, and examples thereof include a polycarbonate resin, an alloy of a polyphenylene ether resin and a polystyrene resin, an alloy of a polyphenylene ether resin and a polyamide resin, a thermoplastic polyester resin, and a methyl group. Methyl acrylate/acrylonitrile/butadiene/styrene copolymer resin, methyl methacrylate/styrene copolymer resin, methyl methacrylate resin, rubber-reinforced methyl methacrylate resin, polyamide resin, Polyacetal resin, polylactic acid based resin, polyolefin resin, and polyphenylene sulfide resin. In the present invention, a polyamide resin, a thermoplastic polyester resin, and a polyphenylene sulfide resin are preferably used, and further preferably a polyamide resin. The thermoplastic resin may be used alone or in combination of two or more.

As the polycarbonate resin, the descriptions of paragraph numbers 0008 to 0013 of JP-A-2008-120866 can be referred to.

As the thermoplastic polyester resin, the descriptions of paragraph numbers 0013 to 0016 of JP-A-2010-174223 can be referred to.

As the polyacetal resin, the descriptions of paragraph numbers 0011 to JP-A-2003-003041 and paragraph numbers 0018 to 0020 of JP-A-2003-220667 can be referred to.

As a polyphenylene sulfide resin, the descriptions of paragraphs 0014 to 0016 of JP-A-10-292114, paragraphs 0011 to 0013 of Japanese Patent Laid-Open No. Hei 10-279800, and Japanese Patent Laid-Open The description of paragraph number 0011 to 0015 of the Japanese Patent Publication No. 2009-30030.

<Inorganic fiber>

The thermoplastic resin composition of the present invention contains inorganic fibers. In the present invention, the Mohs hardness of the LDS additive is 1.5 or more less than the Mohs hardness of the inorganic fiber, that is, the Mohs hardness of the inorganic fiber is 1.5 or more larger than the Mohs hardness of the LDS additive. The difference between the Mohs hardness of the inorganic fiber and the LDS additive is preferably from 1.5 to 6.5, more preferably from 1.5 to 5.5. The inorganic fibers may be used alone or in combination of two or more.

When the thermoplastic resin composition of the present invention is used as an LDS additive, it is preferable to contain an inorganic fiber having a Mohs hardness of 5.5 or more, more preferably an inorganic fiber having a Mohs hardness of 5.5 to 8. Preferably, the inorganic fiber comprises a Mohs hardness of 5.5 to 7.5. With such a configuration, there is a tendency that the effects of the present invention can be exhibited more effectively.

In the thermoplastic resin composition of the present invention, the thermoplastic resin and the inorganic fiber are usually 60% by weight or more of the total components.

<Laser Direct Forming Additive>

The thermoplastic resin composition of the present invention contains at least one of copper, bismuth and tin, and has a Mohs hardness which is 1.5 or more smaller than the Mohs hardness of the inorganic fiber. The LDS additive may be used alone or in combination of two or more.

The LDS additive in the present invention means a compound which is considered to be LDS in relation to 100 parts by weight of PA-MP6 (MAMP6 synthesized in the following examples) resin manufactured by Mitsubishi Gas Chemical Company. 4 parts by weight of the additive of the additive, irradiated with a Yttrium-Aluminum-Garnet Laser having a wavelength of 1064 nm at an output of 10 W, a frequency of 80 kHz, and a speed of 3 m/s. Thereafter, a plating step is performed in a plating bath of an electroless M-Copper 85 manufactured by Mac Dermid, and a plating layer is formed when a metal is applied to the laser irradiation surface. The LDS additive used in the present invention may be a synthetic product or a commercially available product. Further, in addition to being commercially available as an LDS additive, the commercially available product may be a product that is sold as another use as long as it satisfies the requirements of the LDS additive in the present invention. Most of the known LDS additives are black. In the present invention, a non-black LDS additive can also be widely used, so that the resin molded article can be colored.

The Mohs hardness of the LDS additive is preferably from 1.0 to 5.0, more preferably from 2.0 to 5.0. The average particle diameter of the LDS additive is preferably from 0.01 to 50 μm, more preferably from 0.05 to 30 μm. With such a configuration, there is a tendency that the uniformity of the surface state of the plating layer at the time of plating tends to be good.

The blending amount of the LDS additive in the thermoplastic resin composition of the present invention is 1 to 30 parts by weight, preferably 2 to 25 parts by weight, more preferably 3 to 18 parts by weight, per 100 parts by weight of the thermoplastic resin. Again, as described below, by making it In combination with talc, the plating layer can be formed in a small amount.

Hereinafter, preferred embodiments of the LDS additive used in the present invention will be described. By using the LDS additive of such an embodiment, there is a tendency that the effects of the present invention can be exhibited more effectively. However, the invention is of course not limited to the embodiments.

The first embodiment of the LDS additive used in the present invention is a copper-containing LDS additive. In the case of the first embodiment, the content of copper in the metal component in the LDS additive is preferably from 20 to 95% by weight. A preferred example of the copper-containing LDS additive is Cu ₃ (PO ₄ ) ₂ Cu(OH) ₂ .

The second embodiment of the LDS additive used in the present invention is an LDS additive containing bismuth and/or tin. As the metal component, the content of bismuth or tin in the metal component of the LDS additive containing only one of bismuth or tin is preferably from 1 to 95% by weight, more preferably from 1.5 to 60% by weight. In the aspect containing both antimony and tin, the total amount of antimony and tin in the metal component of the LDS additive is preferably 90% by weight or more, more preferably 90 to 100% by weight.

In the second embodiment of the LDS additive, an LDS additive containing bismuth and tin is preferably exemplified. In this embodiment, a more preferable aspect is that both tin and tin are contained, and the content of tin is more than yttrium. Further, it is preferable to contain both bismuth and tin and contain cerium oxide and/or tin oxide, and tin is used. More than 锑.

The LDS additive used in the present invention may, for example, be tin doped with antimony, tin oxide doped with antimony, or tin oxide doped with antimony oxide.

<alkali>

The thermoplastic resin composition of the present invention may also contain a base. When the LDS additive used in the present invention is an acidic substance (for example, a pH of 6 or less), there is a case where the color tone becomes a streak depending on the reduction of the combination itself, but the obtained resin can be formed by adding a base. The color of the product is more uniform. The type of the base is not particularly limited, and calcium hydroxide, magnesium hydroxide or the like can be used. The base may be used alone or in combination of two or more. For example, the above-mentioned copper-containing LDS additive (Cu ₃ (PO ₄ ) ₂ Cu(OH) ₂ ) conforms to an acidic substance LDS additive.

The amount of the base in the thermoplastic resin composition of the present invention is also dependent on the type of the LDS additive and the type of the base, but is preferably from 0.01 to 3% by weight, more preferably from 0.05 to 1% by weight, based on the amount of the LDS additive.

<Inorganic Pigments>

The thermoplastic resin composition of the present invention may also contain an inorganic pigment. In the present invention, the resin molded article can be colored by adding an inorganic pigment. The inorganic pigment may be used alone or in combination of two or more. As the inorganic pigment, an inorganic pigment having an L ^* value of 80 or more and a Mohs hardness of 5.0 or less in CIELab is preferable. The L ^* value is preferably from 50 to 100. The Mohs hardness of the inorganic pigment is more preferably 2 to 5, and further preferably 2.5 to 4.5.

Examples of such an inorganic pigment include ZnS (L ^* value: (87 to 95), Mohs hardness: 3 to 3.5), ZnO (L ^* value: (88 to 96), and Mohs hardness: 4 to 5). It is preferably ZnS.

When a copper-containing additive is used as the LDS additive in the thermoplastic resin composition of the present invention, it is particularly preferred to use a Mohs hardness of 5.0 or less. By using such an inorganic pigment, there is a tendency that the effects of the present invention can be exhibited more effectively.

The amount of the inorganic pigment in the thermoplastic resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 15 parts by weight, still more preferably 0.5 to 12 parts by weight based on 100 parts by weight of the thermoplastic resin composition. Share.

<talc>

The thermoplastic resin composition of the present invention may also contain talc. In the present invention, by blending talc, a suitable plating layer can be formed even if the amount of addition of the LSD additive is reduced.

The amount of the talc in the thermoplastic resin composition of the present invention is preferably from 1 to 20 parts by weight, more preferably from 2 to 15 parts by weight, still more preferably from 2 to 10 parts by weight, per 100 parts by weight of the thermoplastic resin composition. . The blending amount of the LDS additive can be, for example, 1 to 15 parts by weight, and further preferably 1 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin.

The thermoplastic resin composition of the present invention may further contain various additives within the range which does not impair the effects of the present invention. As such additives, there may be mentioned mold release agents, light stabilizers, heat stabilizers, antioxidants, ultraviolet absorbers, flame retardants, dyes, fluorescent whitening agents, anti-dripping agents, antistatic agents, and anti-fogging agents. Agents, lubricants, anti-caking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like.

Further, these components may be used alone or in combination of two or more. The thermoplastic resin composition of the present invention preferably has a Mohs hardness of less than 99% by weight or more of the components other than the inorganic fibers, and more preferably all of the components other than the inorganic fibers have a Mohs hardness lower than that of the inorganic fibers.

<light stabilizer>

Examples of the light stabilizer include a benzophenone compound and a water yang. A compound having an ultraviolet absorbing effect such as an acid ester compound, a benzotriazole compound, or a cyanoacrylate compound, and a compound having a radical scavenging ability such as a hindered amine compound or a hindered phenol compound.

As a light stabilizer, a compound having an ultraviolet absorbing effect and a compound having a radical scavenging ability can be used in combination to exert a higher stabilizing effect.

One type of the light stabilizer may be used, or two or more types may be used in combination.

The benzophenone-based compound is not particularly limited, and examples thereof include 2-hydroxy-4-n-octyloxybenzophenone and 2,2'-dihydroxy-4-methoxybenzophenone. 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone Ketone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone.

The salicylate-based compound is not particularly limited, and examples thereof include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.

The benzotriazole-based compound is not particularly limited, and examples thereof include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(3-tert-butyl-5-). Methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2 '-Hydroxy-5'-trioctylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriene Oxazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di- Third aminophenyl)benzotriazole, 2-{2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5 '-Methylphenyl}benzotriazole, 2,2-methylenebis{4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriene Zin-2-yl)phenol}, and 6-(2-benzotriazolyl)-4-thanooctyl-6'-tert-butyl-4'-methyl-2,2'-methylene Bisphenol and the like.

The cyanoacrylate compound is not particularly limited, and examples thereof include 2-cyano-3,3'-diphenyl 2-ethylhexyl acrylate and 2-cyano-3,3'-di Ethyl phenyl acrylate or the like.

The hindered amine compound is not particularly limited, and examples thereof include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis(2,2,6 succinate). ,6-tetramethyl-4-piperidinyl), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis (1-octyl) sebacate Oxy-2,2,6,6-tetramethyl-4-piperidinyl), n-butyl-3,5-di-t-butyl-4-hydroxybenzylmalonate bis (1, 2,2,6,6-pentamethyl-4-piperidinyl), 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid Condensate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexanediamine and 4-t-octylamino-2,6-dichloro-1 , 3,5-three a linear or cyclic condensate, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl) 4-piperidinyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetra Methylpiper Ketone), 4-benzylidene-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 2-n-butyl 2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonic acid bis(1,2,2,6,6-pentamethylpiperidyl) ester, 3-n-octyl -7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, sebacic acid bis(1-octyloxy-2,2 ,6,6-tetramethylpiperidinyl), bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N,N'-bis (2 ,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedimethylamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidin Pyridyl)-hexanediamine and 4- Lolinyl-2,6-dichloro-1,3,5-three Linear or cyclic condensate, 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidinyl)-1,3,5- three Condensate with 1,2-bis(3-aminopropylamino)ethane, 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6 -pentamethylpiperidinyl)-1,3,5-three a condensate with 1,2-bis-(3-aminopropylamino)ethane, 8-ethylindenyl-3-dodecyl-7,7,9,9-tetramethyl-1, 3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrole Pyridine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidinyl)pyrrolidine-2,5-dione, 4 a mixture of hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N,N'-bis(2,2,6,6-tetramethyl- 4-piperidinyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-tri Condensate, 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-tri And a condensate of 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS registration number [136504-96-6]), 1,6-hexanediamine and 2,4,6 -Trichloro-1,3,5-three , N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine condensate (CAS registration number [192268-64-7]), N-(2 ,2,6,6-tetramethyl-4-piperidinyl)-n-dodecylbutaneimine, N-(1,2,2,6,6-pentamethyl-4-piperidine Base)-n-dodecylbutanediamine, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo - Spiro[4.5]decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5] Reaction product of decane with epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl)-2-(4-methoxyphenyl) Ethylene, N,N'-bis-methylindenyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexanediamine, 4-methoxymethylene Dimer of malonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6 -tetramethyl-4-piperidinyl)]nonane, maleic anhydride-α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2 , 2,6,6-pentamethyl-4-aminopiperidine reaction product, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine) 4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-three , 1-(2-hydroxy-2-methylpropoxy)-4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexyl) )oxymethyl-3,3,5-trimethyl-2- Lulinone, Sanduvor (Clariant; CAS accession number [106917-31-1]), 5-(2-ethylhexyl)oxymethyl-3,3,5-trimethyl-2 - Chlorinone, 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-all three Reaction product with N,N'-bis(3-aminopropyl)ethylenediamine), 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethyl) Piperidin-3-one-4-yl)amino)--three 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperidine -3-keto-4-yl)amino)--three ,N,N',N",N'''-tetra-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) Amino)-three -2-yl)-4,7-diazadecane-1,10-diamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3, 5-three -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido]hexamethylene {(2,2,6,6-tetramethyl-) 4-piperidinyl)imine}], etc., particularly, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2) ,6,6-tetramethyl-4-piperidinyl), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, N,N'-double (2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedimethylamine, N,N',N",N'''-tetra-(4,6- Bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-three -2-yl)-4,7-diazadecane-1,10-diamine, and the like.

The hindered phenol-based compound is not particularly limited, and examples thereof include pentaerythritol-tetrakis {3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, and N,N-hexa. Methylene bis(3,5-di-t-butyl-4-hydroxy-phenylpropanamide), three Ethylene glycol-bis{3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate}, 3,9-bis{2-[3-(3-t-butyl) 4-hydroxy-5-methylphenyl)propynyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, Phosphonic acid 3,5-di-t-butyl-4-hydroxy-benzyl ester-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-third Butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanate, and the like.

<heat stabilizer>

The resin composition of the present embodiment may further contain a heat stabilizer. The heat stabilizer may be selected from the group consisting of a phenol compound, a phosphite compound, a hindered amine compound, and three At least one of a group consisting of a compound and a sulfur-based compound.

One type of the heat stabilizer may be used, or two or more types may be used in combination.

The phenolic compound is not particularly limited, and examples thereof include hindered phenol compounds. Examples of the hindered phenol-based compound include N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide), Pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-third 4-hydroxy-phenylpropanamide), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,9-double {2-[3-(3-Tert-butyl-4-hydroxy-5-methylphenyl)propynyloxy]-1,1-dimethylethyl}-2,4,8,10- Tetraoxaspiro[5.5]undecane, 3,5-di-t-butyl-4-hydroxybenzyl ester-diethyl phosphonate, 1,3,5-trimethyl-2,4,6- Tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl ) Isocyanuric acid, etc.

The phosphite-based compound is not particularly limited, and examples thereof include: Trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, triisodecyl phosphite, phenyl diisononyl phosphite, phenyl diphosphite (13 Alkyl) ester, diphenyl isooctyl phosphite, diphenylisodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris(phenyl) phosphite ) ester, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butyl-5-methylphenyl) phosphite, tris (phosphoric acid) Butoxyethyl) ester, 4,4'-butylene-bis(3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, 4,4'-iso Propylene diphenyl diphosphite tetra(C12-C15 mixed alkyl) ester, bis(nonylphenyl)phosphite 4,4'-isopropylidene bis(2-t-butylphenyl) ester , tris(biphenyl) phosphite, tetrakis(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxyphenyl)butane diphosphite 4,4'-butylenebis(3-methyl-6-tert-butylphenyl)diphosphite tetrakis(tridecyl)ester, 4,4'-isopropylidenediphenyldiphenyl Tetraphosphate (C1~C15 mixed alkyl) ester, triphosphite tris(mono- and di-mixed fluorenyl) Ester, bis(nonylphenyl)phosphite 4,4'-isopropylidene bis(2-tert-butylphenyl) ester, 9,10-di-hydro-9-oxa-9- Oxa-10-phosphaphenanthrene-10-oxide, tris(3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenyl Polyphosphite, bis(octylphenyl). Bis(4,4'-butylene bis(3-methyl-6-t-butylphenyl)). 1,6-hexanol diphosphite, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)diphosphoric acid hexatridecyl ester, sub Tris(4,4'-isopropylidenebis(2-tert-butylphenyl)) phosphate, tris(1,3-stearyloxyisopropyl) phosphite, phosphorous acid 2,2 -methylenebis(4,6-di-t-butylphenyl)octyl ester, 2-ethylhexylphosphite 2,2-methylenebis(3-methyl-4,6-di- Tributylphenyl)ester, 4,4'-extended biphenyl diphosphoric acid Tetrakis(2,4-di-t-butyl-5-methylphenyl) ester, and 4,4'-extended biphenyl diphosphite tetrakis(2,4-di-t-butylphenyl) Ester and the like.

The phosphite-based compound is not particularly limited, and examples thereof include a pentaerythritol-type phosphite compound. Examples of the pentaerythritol type phosphite compound include 2,6-di-t-butyl-4-methylphenyl group. Phenyl. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. methyl. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. 2-ethylhexyl. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. Heterogeneous base. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. Laurel. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. Isotridecyl. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. Stearyl. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. Cyclohexyl. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. Benzyl. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. Ethyl cellosolve. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. Butyl carbitol. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. Octylphenyl. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. Nonylphenyl. Pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylbenzene Base) pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. 2,6-di-t-butylphenyl. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. 2,4-di-t-butylphenyl. Pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl. 2,4-di-third octylphenyl. Pentaerythritol diphosphorus Acid ester, 2,6-di-tert-butyl-4-methylphenyl. 2-cyclohexylphenyl. Pentaerythritol diphosphite, 2,6-di-third amyl-4-methylphenyl. Phenyl. Pentaerythritol diphosphite, bis(2,6-di-third-pentyl-4-methylphenyl)pentaerythritol diphosphite, and bis(2,6-di-th-octyl-4-methyl) Phenyl) pentaerythritol diphosphite, and the like.

As the pentaerythritol type phosphite compound, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-) is preferred. 4-ethylphenyl)pentaerythritol diphosphite, bis(2,6-di-third-pentyl-4-methylphenyl)pentaerythritol diphosphite, and bis(2,6-di-third An octyl-4-methylphenyl)pentaerythritol diphosphite or the like is more preferably a bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

The hindered amine compound is not particularly limited, and examples thereof include 4-ethyloxy-2,2,6,6-tetramethylpiperidine and 4-stearyloxy-2,2,6. 6-Tetramethylpiperidine, 4-propenyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylethenyloxy)-2,2,6,6-tetramethyl Piperidine, 4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyl Oxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6, 6-Tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-(ethylaminemethyloxy)-2,2,6,6-tetramethyl Piperidine, 4-(cyclohexylaminemethyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylaminecarbamoxy)-2,2,6,6- Tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)carbonate, bis(2,2,6,6-tetramethyl-4-piperidine) Ester, bis(2,2,6,6-tetramethyl-4-piperidyl)malonate, bis(2,2,6,6-tetramethyl-4-piperidine) Ester), bis(2,2,6,6-tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-) Tetramethyl-4-piperidinyl), 1,2-bis(2,2,6,6-tetramethyl-4-piperidinyloxy)-ethane, α,α'-bis (2, 2,6,6-Tetramethyl-4-piperidinyloxy)-p-xylene, bis(2,2,6,6-tetramethyl-4-piperidyl)toluene-2,4-diamine Carbamate, bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylene-1,6-dicarbamate, tris (2,2,6, 6-tetramethyl-4-piperidinyl)-benzene-1,3,5-triformate, tris(2,2,6,6-tetramethyl-4-piperidinyl)-benzene-1, 3,4-triformate, 1-[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxy}butyl]-4-[3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propanoxy]2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid and 1 , 2,2,6,6-pentamethyl-4-piperidinol and β,β,β'β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro ( 5,5) a condensate of undecane]diethanol.

As three The compound is not particularly limited, and examples thereof include hydroxyphenyl three. class.

Hydroxyphenyl three For the class, for example, 2,4,6-tris(2'-hydroxy-4'-octyloxy-phenyl)-1,3,5-tri ,2-(2'-hydroxy-4'-hexyloxy-phenyl)-4,6-diphenyl-1,3,5-three , 2-(2'-hydroxy-4'-octyloxyphenyl)-4,6-bis(2',4'-dimethylphenyl)-1,3,5-three ,2-(2',4'-dihydroxyphenyl)-4,6-bis(2',4'-dimethylphenyl)-1,3,5-three , 2,4-bis(2'-hydroxy-4'-propoxy-phenyl)-6-(2',4'-dimethylphenyl)-1,3,5-three , 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4'-methylphenyl)-1,3,5-three , 2-(2'-hydroxy-4'-dodecyloxyphenyl)-4,6-bis(2',4'-dimethylphenyl)-1,3,5-three , 2,4,6-tris(2'-hydroxy-4'-isopropoxyphenyl)-1,3,5-three , 2,4,6-tris(2'-hydroxy-4'-n-hexyloxyphenyl)-1,3,5-three And 2,4,6-tris(2'-hydroxy-4'-ethoxycarbonylmethoxyphenyl)-1,3,5-three Wait.

The sulfur-based compound is not particularly limited, and examples thereof include pentaerythritol tetrakis(3-laurylthiopropionic acid) ester, 3,3′-thiodipropionate dilauryl ester, and 3,3′-thiodi Dimyristyl propionate, and distearyl 3,3'-thiodipropionate.

Next, a step of providing a plating layer on the surface of the resin molded article obtained by molding the thermoplastic resin composition of the present invention will be described with reference to Fig. 1 . Fig. 1 is a schematic view showing a step of forming a plating layer on the surface of a resin molded article 1 by a laser direct structuring technique. In FIG. 1, the resin molded article 1 is a flat substrate, but it is not necessarily a flat substrate, and may be a resin molded article having a part or all of a curved shape. Further, the resin molded article is not limited to the final product, and is intended to include various parts. As the resin molded article of the present invention, a portable electronic machine part is preferable. The portable electronic machine parts have the following features: not only high impact resistance and rigidity, but also excellent heat resistance, and small anisotropy and small warpage, as a PDA for electronic notebooks and portable computers. (Personal Digital Assistant, personal digital assistant), pager (Pocket Bell), mobile phone, PHS (Personal Handy-phone System, personal touch phone system) and other internal structures and housings are extremely effective, especially suitable for molded products A flat-plate portable electronic device component having an average thickness of 1.2 mm or less (the lower limit is not particularly limited, for example, 0.4 mm or more), and is particularly suitable as a casing.

Returning again to Fig. 1, the resin molded article 1 is irradiated with the laser 2. The laser here is not particularly specified, and may be suitably selected from a known laser such as a yttrium aluminum garnet laser, an excimer laser, or a magnet wire, and is preferably a yttrium aluminum garnet laser. Moreover, the wavelength of the laser is not particularly specified, and the preferred wavelength range is 200 to 1200 nm, and particularly preferably 800 to 1200 nm.

When exposed to laser light, the laser-only portion 3 of the resin molded article 1 is activated. The resin molded article 1 is applied to the plating solution 4 in this activated state. The plating solution 4 is not particularly limited, and a known plating solution can be widely used. As the metal component, copper, nickel, gold, silver, or palladium is preferably mixed, and copper is more preferable.

The method of applying the resin molded article 1 to the plating solution 4 is not particularly limited, and examples thereof include a method of introducing it into a liquid in which a plating solution is prepared. The resin molded article after the application of the plating solution forms the plating layer 5 only in the portion irradiated with the laser.

In the method of the present invention, a line pitch of a width of 1 mm or less and further 150 μm or less can be formed (the lower limit is not particularly specified, for example, 30 μm or more). This circuit can be preferably used as an antenna for portable electronic machine parts. In other words, as an example of a preferred embodiment of the resin molded article of the present invention, a plating layer provided on the surface of a portable electronic device component has a resin molded article having an antenna performance.

In addition, Japanese Patent Laid-Open No. 2011-219620, Japanese Patent Laid-Open No. 2011-195820, Japanese Patent Laid-Open No. 2011-178873, and Japanese Patent No. The descriptions of JP-A-2011-168705 and JP-A-2011-148267 are disclosed.

Example

Hereinafter, the present invention will be specifically described by way of examples. The materials shown in the following examples can be appropriately changed without departing from the gist of the present invention. Materials, usage, ratio, processing content, processing steps, etc. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Manufacturing Example 1> (Synthesis of polyamidoamine (PAMP6))

After heating and dissolving adipic acid in a reaction tank under a nitrogen atmosphere, the contents were stirred while p-xylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and isophthalic acid were pressed under pressure (0.35 Mpa). Methylamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) is a 3:7 mixed diamine which is slowly added dropwise in such a manner that the molar ratio of diamine to adipic acid (Rhodia) is about 1:1. At the same time, the temperature is raised to 270 °C. After completion of the dropwise addition, the pressure was reduced to 0.06 MPa for 10 minutes, and the amount of the component having a molecular weight of 1,000 or less was adjusted. Thereafter, the contents were taken out in a strand shape and pelletized in a granulator to obtain polyamine. Hereinafter referred to as "PAMP6".

<Manufacturing Example 2> (Synthesis of polyamine (PAMP10))

After the azelaic acid was heated and dissolved in a reaction tank under a nitrogen atmosphere, the contents were stirred, and p-xylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and isophthalic acid were added under pressure (0.35 MPa). A mixed diamine having a molar ratio of 3:7 in methylamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) is slowly added dropwise in such a manner that the molar ratio of diamine to adipic acid becomes about 1:1, and the temperature is raised to 235 ° C. After completion of the dropwise addition, the reaction was continued for 60 minutes to adjust the amount of the component having a molecular weight of 1,000 or less. After the completion of the reaction, the contents were taken out in a strand form and pelletized in a granulator to obtain polyamine. Hereinafter referred to as "PAMP10".

<Manufacturing Example 3> (Synthesis of polyamine (PAP10))

Weigh accurately weighed sebacic acid (Ito) in a reaction vessel containing a mixer, a condenser, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a strand die with a volume of 50 liters. Made by Oil Co., Ltd., trade name: azelaic acid TA) 8950 g (44.25 mol), calcium hypophosphite 12.54 g (0.074 mol), and sodium acetate 6.45 g (0.079 mol). After sufficiently replacing the inside of the reaction vessel with nitrogen, the mixture was pressurized to 0.4 MPa with nitrogen gas, and the temperature was raised from 20 ° C to 190 ° C while stirring, and the sebacic acid was uniformly melted in 55 minutes. Then, 5960 g (43.76 mol) of p-xylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added dropwise thereto under stirring for 110 minutes. During this time, the temperature in the reaction vessel was continuously increased to 293 °C. The pressure was controlled to 0.42 MPa in the dropping step, and the generated water was removed to the outside of the system through the dephlegmator and the condenser. The temperature of the partial condenser is controlled within the range of 145 to 147 °C. After the dropwise addition of p-xylylenediamine, the polycondensation reaction was continued for 20 minutes under the pressure of 0.42 MPa in the reaction vessel. During this time, the temperature inside the reaction vessel was raised to 296 °C. Thereafter, the pressure in the reaction vessel was reduced from 0.42 MPa to 0.12 MPa in 30 minutes. During this time, the internal temperature was raised to 298 °C. Thereafter, the pressure was reduced at a rate of 0.002 MPa/min, and the pressure was reduced to 0.08 MPa in 20 minutes to adjust the component amount of the molecular weight of 1,000 or less. The temperature in the reaction vessel at the end of the pressure reduction was 301 °C. Thereafter, the inside of the system was pressurized with nitrogen gas, and the polymer was taken out from the strand die in a strand shape under the conditions of a temperature of 301 ° C in the reaction vessel and a resin temperature of 301 ° C and cooled at 20 ° C. The water was cooled and pelletized to obtain about 13 kg of polyamide resin. Further, the cooling time in the cooling water was set to 5 seconds, and the extraction speed of the strands was set to 100 m/min. Hereinafter referred to as "PAP10".

Polyester resin: NOVAPEX (product number: GG500D) (Mitsubishi Chemical)

Polyphenylene sulfide resin (PPS): TORELINA (product number: A670X01(N)) (manufactured by Toray)

<Inorganic fiber>

03T-296GH: Glass fiber (made by Nippon Electric Glass) (Mohs hardness: 6.5)

03T-187: Glass fiber (made by Nippon Electric Glass Co., Ltd.) (Mohs hardness: 6.5)

JA-FT2A: Glass fiber (manufactured by Owens Corning) (Mohs hardness: 6.5)

<LSD Additive>

(1) Lazerflair 8840: Cu ₃ (PO ₄ ) ₂ Cu(OH) ₂ (manufactured by Merck) (Mohs hardness of 5 or less)

(2) Lazerflair 820: a mixture of (Sb/Sn)O ₂ (36-50% by weight) of mica + SiO ₂ (35 to 53% by weight) and TiO ₂ (11 to 15% by weight) (Merck Manufacturing) (Mohs hardness: 5.0 or less)

(3) Black 1G: CuCr ₂ O ₄ (manufactured by Shepherd Color Company) (Mohs hardness of 5.5 to 6)

(4) Black 30C965: CuCr ₂ O ₄ (manufactured by Shepherd color company) (Mohs hardness is 5.5 to 6)

(5) 42-920A: a mixture of Bi ₂ O ₃ (98 to 99% by weight) and Nd ₂ O ₃ (0.3 to 1.0% by weight) (manufactured by East can material) (Mohs hardness: 5.0 or less)

<release agent>

CaV102: manufactured by Clariant Japan (Calmelite Mixture)

405MP: Mitsui Chemicals Manufacturing (polyethylene wax)

<alkali>

Ca(OH) ₂

Mg(OH) ₂

<talc>

Talc: Made by Lin Huacheng, Micron White 5000S

<mixing>

Each component was weighed in a manner as shown in the following table, and the components other than the inorganic fibers were mixed in a drum and charged from the root of a twin-screw extruder (TEM26SS, manufactured by Toshiba Machine Co., Ltd.). The inorganic fibers are introduced into the side to form resin pellets. The temperature setting of the extruder is always set to the same temperature, and the setting is changed according to the type of the resin. It was carried out under the following conditions: 280 ° C for PAMP 6 and PAMP 10 , 300 ° C for PAP 10 , 280 ° C for NOVAPET, and 310 for PPS.

<Manufacture of ISO tensile test piece>

The pellet obtained by the above production method was dried at 80 ° C for 5 hours, and then subjected to an ISO stretching apparatus using an injection molding machine (100T) manufactured by Fanuc Co., Ltd. at a cylinder temperature of 280 ° C and a mold temperature of 130 ° C. The test piece (3 mm thick, 4 mm thick) was injection molded.

Injection speed: The resin flow rate was calculated from the cross-sectional area of the center portion of the ISO tensile test piece, and was set to 300 mm/s. When the filling is about 95%, it is switched to the holding pressure in a manner of changing to VP (Velocity-to-Pressure). The holding pressure was increased within the range where no burrs were present, and the holding pressure was 500 kgf/cm ² for 25 seconds.

<Bending strength and flexural modulus>

The flexural strength (unit: MPa) and the flexural modulus (unit: MPa) were measured according to ISO 178 using the above ISO tensile test piece (4 mm thick) at a temperature of 23 °C.

The Charpy notched impact strength and the Charpy notched impact strength were measured according to ISO 179 using an ISO tensile test piece (3 mm thick) obtained by the above method at 23 °C. The results are shown in the following table.

<plate test>

In a cavity of 100 × 100 mm and a thickness of 2 mm as a mold, a fan-shaped gate having a side of 100 mm and a thickness of 0.8 mm was filled with a resin to be molded. The gate portion was cut off to obtain a flat test piece.

<Uniformity of color of the plate (visual confirmation)>

The flat test piece obtained by the above method was visually confirmed, and the following evaluation was made. The results are shown in the following table.

○: The overall color is uniform

×: Some or all of them have no uniformity.

<plating appearance>

Irradiation of a 10 × 10 mm range of the flat test piece obtained by the above method was carried out using a yttrium aluminum garnet laser having a wavelength of 1064 nm at an output of 10 W, a frequency of 80 kHz, and a speed of 3 m/s. . The subsequent plating step is based on the plating of the electroless M-Copper 85 manufactured by Mac Dermid. Implemented in the tank. The plating performance is to visually judge the thickness of the copper plated at a specific time.

Make the following evaluation. The results are shown in the following table.

◎: Very good appearance (confirm that the color of copper is thicker and covers the thicker plating layer)

○: Good appearance

△: Although it is covered with a plating layer, it is a thinner state (practical level)

×: The state of the plating layer is not completely covered.

It is clear from the above table that a thermoplastic resin composition excellent in any of bending strength, flexural modulus, Charpy impact strength, and plating appearance can be obtained when the LDS additive specified in the present invention is used. (Examples 1-1 to 1-10, 2-1 to 2-5, 3-1 to 3-3).

On the contrary, when the LDS additive having a high Mohs hardness even if it contained copper was used (Comparative Examples 1 to 3, 9, 10), the Charpy impact strength was inferior. On the other hand, in the case of containing no LDS additive but not containing any of copper, bismuth and tin (Comparative Example 4) or completely without the LDS additive (Comparative Examples 5 and 6), the plating appearance Poor. Further, in the case where the glass fiber was not contained (Comparative Examples 7 and 8), the bending strength and the bending elastic modulus were inferior.

Further, when an acidic substance is used as an LDS additive and a base is added At the time (Examples 1-3, 1-4, and 1-7), although the acidic substance was added, the uniformity of the color of the flat plate was achieved. Further, in the present invention, as shown in the following examples, since the coloring can be carried out by the inorganic pigment, the uniformity of the color of the flat plate before coloring need not be too high.

Further, it can be seen that by increasing the blending amount of the LDS additive (Examples 1-5 and 2-3), a better plating appearance can be achieved. It is also known that even if the amount of the LDS additive is not increased, a better plating appearance can be achieved by adding talc (Examples 1-10, 2-5). The reason is that talc absorbs laser light and easily forms a plating layer.

Further, it is understood that the effects of the present invention are particularly effective when a polyamide resin is used as the thermoplastic resin.

<Production of colored particles>

In Examples 1-1 and 2-1, 6 parts by weight of ZnS (L ^* value: 90%, Mohs hardness: 3) was added during mixing, and the same procedure was carried out in the same manner. As a result, the bending strength, the flexural modulus, the Charpy impact strength, and the plating appearance at the same level as in Examples 1-1 and 2-1 were maintained, and particles colored in white were formed.

1‧‧‧Resin molded products

2‧‧‧Laser

3‧‧‧Parts irradiated by laser

4‧‧‧ plating solution

5‧‧‧ plating layer

Fig. 1 is a schematic view showing a step of providing a plating layer on the surface of a resin molded article. In Fig. 1, 1 denotes a resin molded article, 2 denotes a laser, 3 denotes a portion irradiated with laser light, 4 denotes a plating solution, and 5 denotes a plating layer.

1‧‧‧Resin molded product

2‧‧‧Laser

3‧‧‧Parts irradiated by laser

4‧‧‧ plating solution

5‧‧‧ plating layer

Claims (21)

A thermoplastic resin composition for direct laser molding comprising 10 to 150 parts by weight of inorganic fibers and 1 to 30 parts by weight of a laser direct molding additive, and the above-mentioned laser direct molding additive contains copper, with respect to 100 parts by weight of the thermoplastic resin. At least one of cerium, lanthanum and tin and having a Mohs hardness of 1.5 or more less than the Mohs hardness of the inorganic fiber. A thermoplastic resin composition for direct laser molding according to claim 1, wherein the inorganic fiber is a glass fiber. A thermoplastic resin composition for direct laser molding according to claim 1, wherein the thermoplastic resin is a polyamide resin. The thermoplastic resin composition for direct laser molding according to claim 1, which comprises an inorganic pigment having a L ^* value of 80 or more and a Mohs hardness of 1.5 or more in CIELAB with respect to 100 parts by weight of the thermoplastic resin composition. 1 to 20 parts by weight. The thermoplastic resin composition for direct laser molding according to claim 1, which contains 1 to 20 parts by weight of talc per 100 parts by weight of the thermoplastic resin composition. The thermoplastic resin composition for direct laser molding according to claim 1, which comprises 1 to 20 parts by weight of talc, and the amount of the laser direct molding additive is 100 parts by weight based on 100 parts by weight of the thermoplastic resin composition. The serving is 1 to 15 parts by weight. The thermoplastic resin composition for laser direct structuring according to claim 1, wherein the inorganic fiber has a Mohs hardness of 5.5 or more, and the laser direct structuring additive contains copper and has a Mohs hardness of 5.0 or less. The thermoplastic resin composition for laser direct structuring according to claim 7, which further contains a base. The thermoplastic resin composition for laser direct structuring according to claim 7, wherein the inorganic pigment has a Mohs hardness of 5.0 or less. The thermoplastic resin composition for laser direct structuring according to claim 7, wherein the above-mentioned laser direct structuring additive is Cu ₃ (PO ₄ ) ₂ Cu(OH) ₂ . The thermoplastic resin composition for direct laser molding of claim 1, wherein the above-mentioned laser direct structuring additive contains bismuth and tin. The thermoplastic resin composition for laser direct structuring according to claim 11, wherein the above-mentioned laser direct structuring additive contains bismuth and tin, and the content of tin is more than cerium. The thermoplastic resin composition for direct laser molding according to claim 11, wherein the above LDS additive contains cerium oxide and/or tin oxide. The thermoplastic resin composition for laser direct structuring according to claim 13, wherein the laser direct structuring additive contains 36 to 50% by weight of (Sb/Sn)O ₂ , 35 to 53% by weight of a mixture of mica and SiO ₂ , And 11-15% by weight of TiO ₂ . A resin molded article obtained by molding a thermoplastic resin composition for direct laser molding according to claim 1. The resin molded article of claim 15, which comprises a plating layer on the surface. The resin molded article of claim 15, which is a portable electronic machine part. The resin molded article of claim 16, wherein the plating layer has properties as an antenna. A method for manufacturing a resin molded article with a plating layer, comprising the following steps In the case where the surface of the resin molded article obtained by molding the thermoplastic resin composition for direct laser molding of claim 1 is irradiated with a laser, a metal is applied to form a plating layer. A method of producing a resin molded article with a plating layer according to claim 19, wherein the plating layer is a copper plating layer. A method of manufacturing a portable electronic machine component having an antenna, comprising the method of manufacturing a resin molded article of the plating layer of claim 19.